CHEM 234, Spring 2008 Final Exam Ian R.

Gould
PRINTED PRINTED ASU ID or
FIRST NAME LAST NAME Posting ID

Person on your LEFT (or Aisle) Person on your RIGHT (or Aisle)
nomen
1__________/18 reactions
.......................9__________/72.........................
•!PRINT YOUR NAME ON EACH PAGE! synthons
acidity 1
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• READ THE DIRECTIONS CAREFULLY!
acidity 2 pericyclic
3__________/10.........................11__________/20.........................
• USE BLANK PAGES AS SCRATCH PAPER mxns 1
basicity
4__________/12.........................12__________/40.........................
work on blank pages will not be graded...
reactivity
5__________/12 mxns 2
.......................13__________/25.........................
•WRITE CLEARLY! synth 1
basicity 2
6__________/12........................14__________/50.........................
• MOLECULAR MODELS ARE ALLOWED synth 2
malonics
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• DO NOT USE RED INK Stork
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• DON'T CHEAT, USE COMMON SENSE!
Extra Credit_____/5 Total (incl Extra)________/385+5
H He Interaction Energies, kcal/mol
Li Be B C N O F Ne Eclipsing Gauche
Na Mg Al Si P S Cl Ar H/H ~1.0 Me/Me ~0.9
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr H/Me ~1.4 Et/Me ~0.95

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Me/Me ~2.6 i-Pr/Me ~1.1

Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn Me/Et ~2.9 t-Bu/Me ~2.7

O H C N Infrared Correlation Chart Approximate Coupling

small range usually Constants, J (Hz), for
range of values strong
1
N H C O C H NMR Spectra
broad peak C
C 1600–1660 N
C H O H H H
O C C ~7
C H
3300 C
H 2720–2820 C N
3000– 2 peaks O H H H
3100 C 1680
N H 2200 C C ~10 ~8
OR
C H H
broad with spikes ~3300 1735 H
2850–2960
C CH O 1600
C C ~2
O H H
C H
O O
broad ~3300 2200 ~2
C O H C H
1710 NR2 ~15 H
broad ~3000 1650
C C
(cm )-1
3500 3000 2500 2000 1500 H

amine R NH2 variable and condition NMR Correlation Charts –OCH2– O

alcohol R OH dependent, ca. 2 - 6 ! C CH3
–H2C X
O Aromatic Ar H
–H2C NR2
O C H mainly 8 - 6.5 Alkyl
C CH2 C CH 3Y > 2Y > 1Y
R C OH
11 10 9 8 7 6 5 4 3 2 1 0
(!, ppm)
220 O 200 180 160 140 120 100 80 60 40 20 0
R C N –OCH2–
R C OH O Alkyl 3Y > 2Y > 1Y
C R2C CR2 RC CR C X

Aromatic C NR2
CHM 234, Spring 2008, FINAL EXAM - 2- NAME

Question 1 (18 pts.) Provide IUPAC names for the following structures, do not forget to use E/Z
and R/S as appropriate.

a)
CO2H (2S),5-dimethyloct-(5E)-enoic acid

b) ethyl propanoate
O

Question 2 (14 pts.) For the following three structures:

a) Clearly indicate the location of the most acidic hydrogen atom on the line-angle structures
b) Indicate the order of increasing Bronsted acidity for A, B and C. Give a BRIEF explanation.
O O O
H H H
O
O
A B C

A < C < B
least most
acidic acidic

the anion in A is destabilized by the O of the ester, which acts as a resonance

donating group to the enolate anion, the oxygen in B acts as a weak inductive
withdrawing group to the enolate

Question 2 (10 pts.) Rank the following three structures in order of increasing Bronsted acidity.
Give a BRIEF explanation.
O F O O
F
OH OH OH
F
A B C
C < B < A
least most
acidic acidic

the carboxylate is stabilized by the fluorines via the inductive effect, the further the F
from the anion, the weaker the inductive effect
 CHM 234, Spring 2008, FINAL EXAM -3 - NAME

Question 4 (12 pts.) Rank the following in order of increasing basicity, give a BRIEF
explanation.
sp2
sp
sp3 N
N N C
H
A B C

C < A < B
least most
basic basic

non-bonding electrons are lower in energy the more s-character the A.O., lower in energy
means less reactive, less basic

Question 5 (12 pts) Explain why sodium borohydride (NaBH4) will reduce a ketone but will not
reduce an ester. Draw minor resonance structures of the ketone and ester to support your BRIEF
explanation.
O O NaBH4/EtOH OH

O O O O NaBH4/EtOH
no reaction

BH4– is a Lewis base, the carbonyl carbon is Lewis acidic in the ketone (see
resonance structure), the carbonyl carbon is less Lewis acidic in the ester due to
the presence of the oxygen.

Question 6 (12 pts) Give the product of the following acid/base reaction, give a BRIEF explanation
for your choice of product
H
O O
1 Equiv. HCl
O O

the minor resonance contributor shows that the carbonyl

O oxygen has a partial negative charge and is thus more
basic, and the ester oxygen has a partial positive charge
O and is thus less basic
CHM 234, Spring 2008, FINAL EXAM -4- NAME

Question 7. (20 pts.) Provide the reactants that can be used to synthesize the following two
structures using a malonic ester or ethylacetoacetate synthesis, i.e. give the structure of
malonic ester or ethyloacetoacetate and give the structures of the two bromides.

+ Br + EtO2C CO2Et CO2H

Br
malonic ester

O
Br +
+ EtO2C COCH3
Br
Ph
ethyl acetoacetate Ph

Question 8 (18 pts.) Give the reagents/conditions to perform the following alkylation using a Stork
enamine reaction

O 1. N O
Br Br
H
2. BuBr
3. H3O+

b) Give the reagents/conditions to perform the following alkylation using the LDA method, AND give
the unwanted side-product that you would also expect to form under these conditions

O
Br

O
Br
1. 1 Equiv. LDA

2. BuBr
+
O

unwanted side-product
CHM 234, Spring 2008, FINAL EXAM -5- NAME

Question 9 (72 pts)

Provide the missing products, reagents/conditions or reactants, as required. Do not forget
to include stereochemistry as appropriate.

a) 1. excess CH3I
NH2
2. Ag2O/ H2O
3. heat

O HO
EtO– +Na/EtOH
b)
EtO

O O

NH2 1 Equiv. C H3C NH

H3C Cl
c) Ph OH Ph OH

CN
heat
d) +
CN

O
1. H N

e) Cl N
2. LiAlH4
3. H3O+
 -6-
CHM 234, Spring 2008 FINAL EXAM NAME

Question 9, Contd...
Provide the missing products, reagents/conditions or reactants, as required. Do not forget
to include stereochemistry as appropriate.

O Br2/FeBr3 O

f)
Br
O O

OH
O 1. PhMgBr
g)
Ph
2. H3O+

1. Na+ –CN NH2

Br
h)
2. LiAlH4
3. H3O+

1. SO3/H2SO4 NO2
2. H2/Pd/C
NO2
3. HNO3/H2SO4
i)
3. HONO
4. H3PO2 SO3H
CHEMISTRY 234, Spring 2008 FINAL EXAM -7- NAME

Question 10 (22 pts) For EACH of the TWO bonds indicated, A and B, provide the best
SYNTHONS, and also appropriate "actual reagents"

Na+ –OH
OH
Br A (C-O bond) OH

=
B (C-C bond)

Reagents for A Synthons for A

O OH

H
=
MgBr

Reagents for B Synthons for B

Question 11 (20 pts) For the cycloaddition reaction below:

a) Draw the curved arrow-pushing that describes product formation
b) will the stereochemistry of the expected product be cis- or trans-? Give a BRIEF explanation.
Me
Me Me
!
(±) OR (±)

MeO Me MeO Me
MeO Me

TRANS-, this is a 4-electron reaction, the allowed reaction proceeds via a conrotatory Mobius
transition state which puts the methyl groups on opposite sides of the cyclic product

c) Draw the HOMO and LUMO of the reactant cation ON TOP of the structures that are
redrawn below
Me Me

MeO Me MeO Me
HOMO LUMO
CHEMISTRY 234, Spring 2008 FINAL EXAM -8- NAME

Question 12 ( 40 pts.) a) Give a curved arrow-pushing mechanism for the following reactions
• You can give an "abbreviated mechanism, i.e. you may use +H+ and -H+
• BUT, draw all resonance structures for the intermediates
• Add non-bonding electrons and C–H bonds as necessary
O H3O+ O

a) OET OH + HOEt

–H+
+H+
O H O H
H H OH OH
O O

OET OET
OH H
O
O
H H H OH Et
O OH
+H+
–H+ OET
OET
O OH
H H

O OCH3 H3O+
HO H + CH3OH
b)
O
+H+
H H
H
O O O O
O OCH3
H H

H H H H
O OCH3 O OCH3 O OCH3
O
O H H
+H+
H
H H
O OCH3 O OCH3
–H+
O H O
H H
CHEMISTRY 234, Spring 2008 FINAL EXAM -9- NAME

Question13 ( 25 pts.) b) Give a curved arrow-pushing mechanism for the following reaction
• SHOW WHERE EVERY PROTON COMES FROM AND GOES TO (no +H+ or -H+)
• DO NOT DRAW RESONANCE STRUCTURES for the intermediates
• Add non-bonding electrons and C–H bonds as necessary
• At each INTERMOLECULAR step, INDICATE THE Lewis acid and base (LA or LB)
and whether they are also Bronsted acids and bases (BA or BB) as appropriate

O LB/BB
O O
OEt 1. Na+ –OEt/EtOH
O OEt
H
2. H3O+
LA/BA
OEt OH
O

O LA/BA
O H Et
O O
O
LB/BB OEt

OEt
O OH

OEt
O LB/BB
OEt
O O O H O
O
OEt OEt
O
LB/BB LA/BA
H O OH
LA/BA O
Et

Extra Credit Question (5 pts). Hydrolysis of which functional groups is used to make soap?

amine ester amide aldehyde

 CHM 234, Spring 2008 FINAL EXAM - 10 - NAME

Question 14 (50 pts.) Show how you would make the target componds on the right form the
starting compounds on the left. Show reagents and conditions where appropriate, and the
structures of important intermediate compounds. Do not show any (arrow pushing)
mechanisms. For question a) you must indicate steps that require separation of isomers

Cl
a)
Br
HNO3/H2SO4 NH2

Br2/FeBr3

separate Cl
isomers
Cl2/AlCl3
Cl
NO2
H2/Pd/C NH2

NO2

THE NEXT TWO SYNTHESIS PROBLEMS, b) and c), USE ONLY THE "SIMPLE SET OF
REACTIONS" PROVIDED RECENTLY ON THE CLASS WEB PAGE!

O OH
Br Mg.THF MgBr 1.
HBr H
b)
ROOR 2. H3O+

Ph
c)
O

1. Hg(OAc)2/H2O PCC
2. NaBH4/EtOH

H 1. PhMgBr Ph
PCC

OH O 2. H3O+ OH
CHM 234, Spring 2008 FINAL EXAM - 11 - NAME

Question 15 (40 pts.) In each case, synthesize the (target) molecules on the right from the
starting molecules the left. this can not be done in one reaction. Give reagents and conditions
and the intermediate molecules at each step. Do not show any mechanisms or transient
intermediates.

O N
a)

Br2, h!

Br

HN(CH3)2

COCl
MgBr CO2H
Mg . THF
1. CO2 SOCl2

2. H3O+

b) OH OH
HO N
(ignore stereochemistry) H

NaBH4
PCC
EtOH
O
O
O H N H
H

1 Equiv. H+

H3O+
HO OH

O O MeNH2 / H+
O O O
N
H H2/Pd/C H H